Plastic modifiers

ABSTRACT

Hydrocarbyl terminated polyester compounds comprising sulfur-containing repeat units that are useful as plastic modifiers, polymer blend compositions comprising the hydrocarbyl terminated polyester compounds, methods for modifying the performance properties of polymers, and methods for preparing the hydrocarbyl terminated polyester compounds.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.15/148,378, filed May 6, 2016, which claims the priority of U.S.provisional Application No. 62/158,112, filed May 7, 2015, thedisclosure of each is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to hydrocarbyl terminatedpolyester compounds having sulfur-containing repeat units that areuseful as plastic modifiers. In particular, the disclosure relates tothe polyester compounds, polymer blends comprising polymers and thepolyester compounds, and methods of using the polyester compounds tomodify performance properties of polymers.

BACKGROUND OF THE INVENTION

Non-biodegradable polymers, such as polyvinyl chloride (PVC), are usedin a wide variety of consumer products. The functional properties ofmany polymers can be improved by the addition of additives such asplasticizers. Phthalates are the most commonly used plasticizers, buttheir use is being phased out because of concerns about health andenvironmental risks. Thus, there is a need for new functional andenvironmentally friendly plasticizers that provide the same performancebenefits as phthalates and/or improve the performance properties ofpolymers such as PVC. For biodegradable polymers made from polylactide(PLA), a plasticizer is appreciated in terms of improving PLAperformances and reducing production cycle time without sacrificingbiodegradability of the end consumer products.

SUMMARY OF THE INVENTION

Among the various aspects of the present disclosure is the provision ofa polyester composition comprising compounds of Formula (I):

wherein:

-   -   R¹ and R³ independently are hydrocarbyl or substituted        hydrocarbyl;    -   R² is R⁴CO— or R⁴, wherein R⁴ is hydrocarbyl or substituted        hydrocarbyl;    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

Another aspect of the present disclosure encompasses a polymer blendcomposition comprising a polymer and a polyester composition comprisingcompounds of Formula (I):

wherein:

-   -   R¹ and R³ independently are hydrocarbyl or substituted        hydrocarbyl;    -   R² is hydrogen, R⁴CO—, or R⁴, wherein R⁴ is hydrocarbyl or        substituted hydrocarbyl;    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

A further aspect of the present disclosure provides a process formodifying performance properties of polymers. The process comprisescontacting a polymer with a polyester composition comprising compoundsof Formula (I) to form a polymer blend composition, wherein the polymerblend composition has an improved performance property relative to anunmodified polymer, the compounds of Formula (I):

wherein:

-   -   R¹ and R³ independently are hydrocarbyl or substituted        hydrocarbyl;    -   R² is hydrogen, R⁴CO—, or R⁴, wherein R⁴ is hydrocarbyl or        substituted hydrocarbyl;    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

Still another aspect of the present disclosure encompasses a process forpreparing a polyester composition comprising compounds of Formula (Ia)from a compound of Formula (III). The process comprises (a) contactingthe compound of Formula (III) with an alcohol, R³OH, to form adistribution of compounds of Formula (II) and (b) contacting thedistribution of compounds of Formula (II) with an acyl halide or itsacid analog, R⁴C(O)X, to form the polyester composition comprisingcompounds of Formula (Ia), according to the following reaction scheme:

wherein:

-   -   R¹, R³, and R⁴ independently are hydrocarbyl or substituted        hydrocarbyl;    -   X is a halide ion or a hydroxyl group;    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

Yet another aspect of the present disclosure provides a processpreparing a polyester composition comprising compounds of Formula (Ia)from a compound of Formula (IV). The process comprises (a) contactingthe compound of Formula (IV) with an alcohol, R³OH, to form adistribution of compounds of Formula (II) and (b) contacting thedistribution of compounds of Formula (II) with an acyl halide or itsacid analog, R⁴C(O)X, to form the polyester composition comprisingcompounds of Formula (Ia), according to the following reaction scheme:

wherein:

-   -   R¹, R³, and R⁴ independently are hydrocarbyl or substituted        hydrocarbyl;    -   X is a halide ion or a hydroxyl group;    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

Other features and iterations of the invention are described in moredetail below.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure provides hydrocarbyl terminated polyestercompounds comprising sulfur-containing repeat units that are useful asplastic modifiers. In particular, the polyester compounds disclosedherein can be used to modify the performance properties of industrialplastics. For example, the polyester compounds can improve theflexibility and/or impact properties of polymers. Additionally, thepolyester compounds disclosed herein have low migration and lowtoxicity. The present disclosure also provides polymer blends comprisingpolymers and the polyester compounds, as well as processes for preparingthe polyester compounds.

(I) Polyester Compounds

(a) Structure

One aspect of the present disclosure provides a polyester compositioncomprising compounds of Formula (I):

wherein:

-   -   R¹ and R³ independently are hydrocarbyl or substituted        hydrocarbyl;    -   R² is hydrogen, R⁴CO—, or R⁴, wherein R⁴ is hydrocarbyl or        substituted hydrocarbyl    -   Z is sulfur, sulfoxide, or sulfone;    -   k is an integer of 1 or greater; and    -   n is an integer of 1 or greater.

In various embodiments, R¹ may be alkyl, alkenyl, alkynyl, aryl,substituted alkyl, substituted alkenyl, substituted alkynyl, orsubstituted aryl. Additionally, R¹ in each repeat unit may differ. Insome embodiments, R¹ may be C₁ to C₆ alkyl or C₁ to C₆ alkenyl, whereinalkyl and alkenyl may be linear, branched, or cyclic. In certainembodiments, R¹ may be methyl, ethyl, propyl, isopropyl, butyl,tert-butyl, hexyl, cyclohexyl, and the like. In specific embodiments, R¹may be methyl.

In certain embodiments, R² may be R⁴CO—, wherein R⁴ may be alkyl,substituted alkyl, alkenyl, substituted alkenyl, aryl, or substitutedaryl, and alkyl or alkenyl may be linear or branched. In someembodiments in which R² is R⁴CO—, R⁴ may be C₁ to C₃₀ alkyl or C₁ to C₃₀alkenyl. In other embodiments in which R² is R⁴CO—, R⁴ may be C₁ to C₂₂alkyl or C₁ to C₂₂ alkenyl. In further embodiments in which R² is R⁴CO—,R⁴ may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, ordocosanyl. In other embodiments, R² may be R⁴, wherein R⁴ may be alkyl,substituted alkyl, alkenyl, substituted alkenyl, aryl, or substitutedaryl, wherein alkyl and alkenyl may be linear or branched. In someembodiments in which R² is R⁴, R⁴ may be C₁ to C₃₀ alkyl or C₁ to C₃₀alkenyl. In other embodiments in which R² is R⁴, R⁴ may be C₁ to C₂₂alkyl or C₁ to C₂₂ alkenyl. In further embodiments in which R² is R⁴, R⁴may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, ordocosanyl. In still other embodiments, R² may be hydrogen.

In some embodiments, R³ may be alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, or substituted aryl, wherein alkyl andalkenyl may be linear or branched. In certain embodiments, R³ may be C₁to C₃₀ alkyl, or C₁ to C₃₀ alkenyl. In other embodiments, R³ may be C₁to C₂₂ alkyl or C₁ to C₂₂ alkenyl. In particular embodiments, R³ may bemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, ordocosanyl.

In some embodiments, Z may be sulfoxide. In other embodiments, Z may besulfone. In specific embodiments, Z may be sulfur.

In some embodiments, n may be an integer from 1 to 20, from 1 to 10, orfrom 1 to 6. In certain embodiments, n may be 1, 2, 3, or 4. In specificembodiments, n may be 2.

In general, k may range from 1 to several thousand. In some embodiments,k may range from 1 to about 500, from 1 to about 100, from 1 to about50, or from 1 to about 20. In certain embodiments, k may range from 1 to10, from 1 to 9, from 1 to 8, from 1 to 7, from 1 to 6, from 1 to 5,from 1 to 4, or from 1 to 3. While it is understood that polyestersembody a distribution of molecules, individual molecules also areincluded in this disclosure (i.e., k is 1, k is 2, k is 3, and thelike).

In exemplary embodiments, R¹ is methyl; R² is R⁴CO— or R⁴, wherein R⁴ isalkyl, substituted alkyl, alkenyl, or substituted alkenyl; R³ is alkyl,substituted alkyl, alkenyl, or substituted alkenyl; n is 2; k rangesfrom 1 to 20; and Z is sulfur.

(b) Stereochemistry

The polyester compounds having Formula (I) disclosed herein generallyhave at least one chiral center, as denoted with an asterisk in theschematic below

wherein R¹, R², R³, Z, n, and k are as defined above. The compoundsdisclosed herein may comprise additional chiral centers.

Each chiral center may have an R or an S configuration. In compoundscomprising one chiral carbon, the configuration may be R or S. Incompounds comprising two or more chiral carbons, the configuration ofeach will be independently R or S. For example, in compounds comprisingtwo chiral carbons, the configuration may be RR, RS, SR, or SS, incompounds comprising three chiral carbons, the configuration may be RRR,RRS, RSR, RSS, SRR, SRS, SSR, or SSS, and so forth.

(c) Properties

The polyester compounds disclosed herein represent a distribution ofcompounds having different numbers of repeat units. In general, thepolyester compounds of Formula (I) have a number average molecularweight (M_(n)) of about 100 g/mol to about 200,000 g/mol. In someembodiments, the number average molecular weight of compounds of Formula(I) may range from about 100 g/mol to about 300 g/mol, from about 300g/mol to about 1000 g/mol, from about 1000 g/mol to about 3000 g/mol,from about 3000 g/mol to about 10,000 g/mol, from about 10,000 g/mol toabout 30,000 g/mol, from about 30,000 g/mol to about 100,000 g/mol, orgreater than about 100,000 g/mol. In certain embodiments, the numberaverage molecular weight of the compounds of Formula (I) may range fromabout 150 g/mol to about 5000 g/mol, from about 300 g/mol to about 4000g/mol, from about 600 g/mol to about 3000 g/mol, or from about 800 g/molto about 2000 g/mol.

In general, the polyester compounds disclosed herein are substantiallybiodegradable and compostable (per ASTM D6400), have low volatility, lowtoxicity, and/or can be used as flame retardants. As detailed below, thepolyester compounds disclosed herein may be used as plasticizers toincrease the flexibility and durability of polymers.

(II) Polymer Blend Compositions

(a) Components

Another aspect of the present disclosure encompasses polymer blendcompositions comprising polymers and polyester compounds of Formula (I).The polyester compounds are defined above in section (I). The polyestercompounds of Formula (I) function as modifiers to improve one or moreperformance properties of polymers, such as, for example, increasing theflexibility and/or durability.

The identity of the polymer in the polymer composition can and willvary. In general, the polymer may be a thermoplastic polymer. In variousembodiments, the polymer may be polyvinyl chloride, polylactide,poly(acrylic acid), poly(methacrylic acid), poly(methyl acrylate),poly(methyl methacrylate), poly(vinyl acetate), poly(vinyl alcohol),polyethylene, polystyrene, polypropylene, polycaprolactone,polyhydroxyalkanoate, polyurethane, cellulosics, polyacetal, polyamide,polyamine-imide, polyacrylonitrile, polybutadiene, polybutylene,polycarbonate, polydicyclopentadiene, polyketone, polyester,polyetheretherketone, polyetherimide, polyetheylenchlorinate, polyimide,polymethylpentene, polyethylene oxide, polyphenylene oxide,polyphenylene sulfide, polyphthalamide, polysulfone, silicone,copolymers thereof (e.g., acrylonitrile-butadiene-styrene, vinylchloride-vinyl acetate, vinyl chloride-acrylate, vinylchloride-methacrylate, etc.), or combinations of any of theaforementioned polymers. In specific embodiments, the polymer may bepolyvinyl chloride (PVC) or polylactide (PLA).

The amount of the polyester compounds of Formula (I) included in thepolymer blend compositions can and will vary. In some embodiments, theamount of the polyester compounds having Formula (I) included in thepolymer blend composition may range from about 1 to about 100 parts byweight per hundred parts by weight of the polymer or resin (pphr). Invarious embodiments, the amount of the polyester compounds havingFormula (I) present in the polymer blend composition may range fromabout 1 to about 3 pphr, from about 3 to about 10 pphr, from about 10 toabout 30 pphr, or from about 30 to about 100 pphr. In other embodiments,the amount of the polyester compounds of Formula (I) included in thepolymer blend composition may range from about 1 wt % to about 70 wt %by weight of the polymer blend composition. In certain embodiments, theamount of the polyester compounds of Formula (I) included in the polymerblend composition may range from about 1 wt % to about 3 wt %, fromabout 3 wt % to about 10 wt %, from about 10 wt % to about 30 wt %, orfrom about 30 wt % to about 70 wt % by weight of the polymer blendcomposition.

In embodiments in which the polymer blend composition comprises PVC, theamount of the polyester compounds of Formula (I) included in the PVCblend composition may range from about 5 to about 100 pphr. In variousembodiments, the amount of the polyester compounds having Formula (I)included in the PVC blend composition may range from about 5 to about 10pphr, from about 10 to about 20 pphr, from about 20 to about 30 pphr,from about 30 to about 40 pphr, from about 40 to about 50 pphr, fromabout 50 to about 60 pphr, from about 60 to about 70 pphr, from about 70to about 80 pphr, from about 80 to about 90 pphr, or from about 90 toabout 100 pphr.

In embodiments in which the polymer blend composition comprises PLA, theamount of the polyester compounds having Formula (I) included in the PLAblend composition may range from about 5 wt % to about 50 wt % by weightof the PLA blend polymer composition. In certain embodiments, the amountof the polyester compounds of Formula (I) present in the PLA blendcomposition may range from about 5 wt % to about 10 wt %, from about 10wt % to about 15 wt %, from about 15 wt % to about 20 wt %, from about20 wt % to about 25 wt %, from about 25 wt % to about 30 wt %, fromabout 30 wt % to about 40 wt %, or from about 40 wt % to about 50 wt %by weight of the PLA blend polymer composition.

(b) Properties of the Polymer Blend Compositions

The polymer blend compositions disclosed herein generally have lowerglass transition temperatures (T_(g)) than those of unblended (orpristine) polymers. That is, the addition of polyester compounds ofFormula (I) to a polymer reduces the T_(g) of the polymer, therebyimproving the flexibility and/or impact properties of the polymer. Ingeneral, the reduction in T_(g) of the polymer blend compositionsdisclosed herein is correlated with the amount of the polyestercompounds of Formula (I) incorporated into the polymer blendcomposition. For example, the T_(g) of a polymer blend composition canbe reduced to below room temperature simply by adding a sufficientamount of polyester compounds of Formula (I). The T_(g) of the polymerblend compositions disclosed herein may be reduced by about 5° C. toabout 10° C., by about 10° C. to about 20° C., by about 20° C. to about30° C., by about 30° C. to about 40° C., by about 40° C. to about 50°C., by about 50° C. to about 60° C., or more than 60° C. relative to theT_(g) of unblended polymers.

Additionally, the polymer blend compositions comprising PLA disclosedherein may have reduced cold crystallization temperature (T_(cc)) ascompared to the T_(cc) of unblended (or original) polymers. In general,the PLA polymer blend compositions disclosed herein have a significantdrop of T_(cc), which suggests an efficient plasticization andpotentially increased crystallization rate during processing of the PLApolymer blend compositions. Thus, end products comprising PLA polymerblend compositions disclosed herein may have reduced production cycletimes, with the end products having good crystallinity. In someembodiments, the T_(cc) of the PLA polymer blend composition may bereduced by about 5° C. to about 10° C., by about 10° C. to about 20° C.,by about 20° C. to 30° C., by about 30° C. to about 40° C., by about 40°C. to about 50° C., by about 50° C. to about 60° C., or more than about60° C. as compared to the T_(cc) of unblended polymers.

Furthermore, the polymer blend compositions disclosed herein may haveincreased elongation at break as compared to that of unblended polymers.Typically, the polymer blend compositions disclosed herein have at leasta 1.1-fold increase in elongation at break as compared to that ofunblended polymers. In various embodiments, the elongation at break ofthe polymer blend compositions disclosed herein may be increased fromabout 1.1 to about 3-fold, from about 3-fold to about 10-fold, fromabout 10-fold to about 30-fold, from about 30-fold to about 100-fold,from about 100-fold to about 300-fold, or more than about 300-fold ascompared to the elongation at break of unblended polymers. The polymerblend compositions also may have various (elongation) percentages atbreak. In some embodiments, the percentage at break may be from about 1to about 10%, from about 10 to about 30%, from about 30 to about 100%,from about 100 to about 300%, from about 300 to about 1000%, or morethan about 1000%.

The polymer blend compositions disclosed also may have reduced tensilemodulus as compared to that of unblended polymers. In general, thepolymer blend compositions disclosed herein have at least a 1% reductionin tensile modulus as compared to that of unblended polymers. In variousembodiments, the tensile modulus of the polymer blend compositionsdisclosed herein may be reduced from about 1 to about 10%, from about 10to about 20%, from about 20 to 30%, from about 30 to about 40%, fromabout 40 to about 50%, from about 50 to about 60%, from about 60 toabout 70, from about 70 to about 80%, or more than about 80% as comparedto the tensile modulus of unblended polymers.

The polymer blend compositions disclosed also may have reduced tensilestrength at break as compared to that of unblended polymers. In general,the polymer blend compositions disclosed herein have at least a 1%reduction in tensile strength at break as compared to that of unblendedpolymers. In various embodiments, the tensile strength at break of thepolymer blend compositions disclosed herein may be reduced from about 1to about 10%, from about 10 to about 20%, from about 20 to 30%, fromabout 30 to about 40%, from about 40 to about 50%, from about 50 toabout 60%, from about 60 to about 70, from about 70 to about 80%, ormore than about 80% as compared to the tensile strength at break ofunblended polymers.

(c) Optional Additives

The polymer blend compositions detailed above may further comprise atleast one additive. Non-limiting examples of suitable additives includeheat stabilizers, UV/light stabilizers, flame retardants/smokesuppressors, antioxidants, biocides, processing aids, thermal modifiers,impact modifiers, blowing agents, fillers, lubricants/co-stabilizers,pigments, and nucleating agents.

In some embodiments, the polymer blend composition may further comprisea heat stabilizer. Heat stabilizers generally comprise metal compoundssuch as metal soaps, metal salts, and organometallic compounds. Themajor metals contained in heat stabilizers include calcium, tin, zinc,barium, and lead. Non-limiting examples of suitable heat stabilizersinclude calcium-zinc stabilizer, calcium-organic stabilizer, (e.g.,calcium acetylacetonate, zinc acetylacetonate), calcium stearate, zincstearate, methyl tin stabilizer, organotin mercaptides, and combinationsthereof.

In other embodiments, the polymer blend composition may further comprisea UV stabilizer or light stabilizer. Suitable UV stabilizers or lightstabilizers include, without limit,2-(2′-hydroxy-5′-methylphenyl)-benzotriazole, 2-hydroxy-4-octoxybenzophenone, 2-(2′-hydroxy-5′-tert-octylphenyl) benzotriazole,2-(2′-hydroxy-3,5′-ditert-butylphenyl)-benzotriazole,2-(2′-hydroxy-3,5′-ditert-butylphenyl)-5-chloro benzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chloro benzotriazole,2-hydroxy-4-methoxy benzophenone,poly[1-(2′-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidylsuccinate, bis(2,2,6,6,-tetramethyl-4-piperidine) sebacate,2-hydroxy-4-methoxy benzophenone-5-sulfonic acid,2-phenyl-1H-benzo[d]imidazole-5-sulfonic acid,2-(2′-hydroxy-3′-5′-ditert-butyl) benzotriazole,2,2′-dihydroxy-4-methoxy benzotriazole, hindered amine light stabilizers(HALS), titanium dioxide and combinations thereof.

In still other embodiments, the polymer blend composition may furthercomprise a fire retardant or smoke suppressor. Non-limiting examples ofsuitable fire retardants/smoke suppressants include alumina trihydrate,magnesium hydroxide, antimony trioxide, hydromagnesite, copper clays,molybdates, borates, chlorendic acid derivatives, chlorinated paraffins,decabromodiphenyl ether, decabromodiphenyl ethane, brominatedpolystyrenes, brominated epoxy oligomers, tetrabromophthalic anhydride,tetrabisphenol A, hexabromocyclododecane, triphenyl phosphate,resorcinol bis(diphenylphosphate, bisphenol A diphenyl phosphate,tricresyl phosphate, dimethyl methyphosphonate, alumina diethylphosphinate, tris(2,3-dibromopropyl phosphate,tris(1,3-dichloro-2-prpyl)phosphate,(2-chlorethyl)dichloroisopentyldiphosphate, and combinations thereof.

In further embodiments, the polymer blend composition may furthercomprise an antioxidant. Suitable antioxidants include without limittetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,octadecyl 3-(3,5-tertiary butyl-4-hydroxyl phenyl)propionate,tris-(2,4-tert-butylphenyl)phosphite, didodecyl 3,3-thiodipropinate,bis(2,4-dicumylphenyl)pentaerythritol diphosphite, hindered phenols,secondary aromatic amines, benzofuranones, and combinations thereof.

In other embodiments, the polymer blend composition may further comprisea biocide. Non-limiting examples of suitable biocide include copper2-ethylhexanoate, zinc pyrithione, 10,10′-oxybisphenooxyarsine,diodomethyl-p-tolylsulfone, 3-iodo-2-propynyl butylcarbamate,N-(trichloromethylthio)phthalimide, n-octyl-, dichloron-ocyl-isothiazolinone, butylbenzisothiazolinone, and combinationsthereof.

In yet other embodiments, the polymer blend composition may furthercomprise a processing aid. Processing aids include, but are not limitedto, acrylic processing aids, acrylate copolymers, styrene-acrylonitrilecopolymers, methylmethacylate-styrene-vinylacetate copolymers, andcombinations thereof.

In further embodiments, the polymer blend composition may furthercomprise a thermal modifier. Non-limiting examples of suitable thermalmodifiers include methyacrylate-butadiene-styrene terpolymers (e.g.,Clearstrength E-920), acrylonitrile-butadiene-styrene copolymers,alpha-methylstyrene copolymers, ethylene-propylene copolymers, ethylenecopolymers, acrylate modifiers (e.g., phenoxyethyl methacrylate,ethylene glycol dimethacrylate, dimethacrylate, 1,3-butylene glycol,hexanediol dimethacrylate, trimethyacrylate ester, trimethyacrylate,trimethylolpropane), and combinations thereof.

In still other embodiments, the polymer blend composition may furthercomprise an impact modifier. Impact modifiers include without limitethylene copolymers, ethylene/butyl acrylate/glycidyl methacrylatecopolymers, ethylene-propylene copolymers, acrylic impact modifiers,acrylonitrile-butadiene-styrene copolymers,acrylonitrile-styrene-acrylate copolymers, styrene-butadiene-styrenecopolymers, styrene-ethylene-butadiene-styrene copolymers, chlorinatedpolyethylene, crosslinked polyacrylate, and combinations thereof.

In alternate embodiments, the polymer blend composition may furthercomprise a blowing agent. Non-limiting examples of suitable blowingagents include azodicarbonamide or other azo-based compounds, hydrazinenitrate or other hydrazine-based compounds, endothermic chemical foamingagents (CFAs), exothermic CFAs, endothermic/exothermic CFA blends,hydrocarbons (e.g., pentane, isopentane, cyclopentane), isocyanate, andcombinations thereof.

In other embodiments, the polymer blend composition may further comprisea lubricant or co-stabilizer. Suitable lubricants or co-stabilizersinclude without limit polyols, epoxidized esters, epoxidized oils,polyethylene waxes, oxidized polyethylene waxes, paraffins, metallicsoaps (e.g., calcium stearate, zinc stearate, etc.), esters (e.g.,polyethylene mono/di/tri stearate, glycerol monostearate, glycerylmonooleate, Montan wax, stearyl stearate, distearyl phthalate), amides(e.g., erucamide, oleamido, stearamide, ethylene bis(stearamide), and soforth), fatty acids (e.g., lauric acid, stearic acid, oleic acid, etc.),fatty alcohols (e.g., cetyl alcohol, stearyl alcohol, behenoyl alcohol,and so forth), and combinations thereof.

In further embodiments, the polymer blend composition may furthercomprise a filler. Non-limiting examples of suitable fillers includecalcium carbonate, titanium dioxide, calcinated clay, glass, talc, mica,red mud, dolomite, and combinations thereof.

In still other embodiments, the polymer blend composition may furthercomprise a pigment. Suitable pigments include without limit titaniumoxide, carbon black, jet black, red iron oxide, yellow iron oxide,benzimidazalone yellow, ultramarine violet, ultramarine blue, greenpigment, orange pigment, and combinations thereof.

In embodiments in which the polymer blend composition comprises PLA, thecomposition may further comprise a nucleating agent. Non-limitingexamples of suitable nucleating agents includeN,N′-ethylene-bis-stearamide (EBS), LAK-301 (an aromatic sulfonatederivative), talc, sodium benzoate, calcium carbonate, calcium salts ofsuberic acid, calcium salts of pimelilc acid, beta-cyclodextrin,polyoxymethylene, magnesium, sodium, or zinc phenylphosphonate, cyanuricacid, uracil, thymine, nitroimidazole, and fatty acid amides.

The concentration of each optional additive in the polymer blendcomposition can and will vary. In general, the concentration of eachadditive may range from about 0.001 wt % to about 10 wt % of the polymerblend composition. In various embodiments, the concentration of eachadditive may range from about 0.001 wt % to about 0.01 wt %, from about0.01 to about 0.1 wt %, from about 0.1 to about 1 wt %, or from about 1to about 10 wt % of the polymer blend composition.

(d) Methods for Preparing Polymer Blend Compositions

The polymer blend compositions disclosed herein may be prepared usingcompounding methods that are well known to those skilled in the art. Insome embodiments, the polymer blend compositions may be prepared byblending all the ingredients using a high-speed mixer or a ribbonblender. In other embodiments, the polymer blend compositions may beprepared by blending all the ingredients and then transferring the blendto a compounding extruder to produce a melt extrusion, which then can becut into granules or pellets. The resultant polymer blend compositionmay be a powder, a granular material, or a pelletized material.

(III) Processes for Modifying Polymer Properties

Another aspect of the disclosure provides processes for improvingperformance properties of polymers. The processes comprise contactingpolymers with polyester compounds of Formula (I) to form polymer blendcompositions, wherein the polymer blend compositions have improvedperformance properties as compared to unblended polymers.

In some embodiments, the polymer blend composition has increasedflexibility as compared to unblended (or unmodified) polymers. In otherembodiments, the polymer blend composition has a reduced glasstransition temperature as compared to unmodified polymer. In furtherembodiments, the polymer blend composition has a reduced coldcrystallization temperature as compared to the unmodified polymer. Instill other embodiments, the polymer blend composition has an increasedelongation at break as compared to the unmodified polymer. In additionalembodiments, the polymer blend composition has decreased tensilestrength as compared to the unmodified polymer. In yet otherembodiments, the polymer blend composition has decreased tensilestrength at break as compared to the unmodified polymer. In alternateembodiments, the polymer blend composition has reduced hardness ascompared to the unmodified polymer. In still other embodiments, thepolymer blend composition has increased tear strength as compared to theunmodified polymer. In embodiments in which the polymer blendcomposition comprises PLA, the polymer blend composition has a reducedcycle time for production of end products comprising PLA.

Polyester compounds having Formula (I) are detailed above in section(I); suitable polymers are described above in section (II)(a), the ratioof the polyester compounds to the polymer is detailed above in section(II)(a), means for contacting the polymer with the polyester compoundsare described above in section (II)(d).

(IV) Processes for Preparing Polyesters

Still another aspect of the present disclosure encompasses processes forpreparing polyester compounds of Formula (I). Persons skilled in the artunderstand that a variety of different processes may be used to preparethe polyester compounds disclosed herein. Several processes aredescribed below. In general, the processes comprise two steps. Step Aentails an esterification/polymerization reaction that may be mediatedby condensation or ring opening polymerization. Step B comprises anesterification or an alkylation reaction, thereby forming thehydrocarbyl terminated polyester compounds disclosed herein.

(a) Step A—Condensation

In some embodiments, the esterification/polymerization step is performedby condensation. Thus, step A comprises contacting a compound of Formula(III) with an alcohol, R³OH, to form a distribution of compounds ofFormula (II) in which k varies. The reaction is diagrammed below:

wherein R¹, R³, Z, k, and n are as defined above in section (I).

The condensation reaction comprises contacting the compound of Formula(III) with an alcohol (R³OH). The amount of alcohol that is contactedwith the compound having Formula (III) can and will vary. In general,the mole-to-mole ratio of the compound having Formula (III) to R³OH mayrange from about 1:0.1 to about 1:10. In various embodiments, themole-to-mole ratio of the compound having Formula (III) to R³OH mayrange from about 1:0.2 to about 1:8, from about 1:0.4 to about 1:6, fromabout 1:0.6 to about 1:5, from about 1:0.8 to about 1:4, from about1:0.9 to about 1:3, or from about 1:1 to about 1:2.

In general, contact between the compound of Formula (III) and thealcohol is conducted in the presence of a catalyst. The catalyst may bea chemical catalyst, such as a proton donor, an organometallic compound,such as tin compounds, or another chemical catalyst known in the art.Alternatively, the catalyst may be an enzyme catalyst, such as a lipaseenzyme. Lipase enzymes can catalyze the formation (as well ashydrolysis) of ester linkages.

In embodiments in which the catalyst is a proton donor, a variety ofproton donors may be used in the process. Non-limiting examples ofsuitable proton donor include acid salts (e.g., bisulfates,hydrosulfates), mineral acids (e.g., hydrogen halides such ashydrochloric acid, hydrobromic acid; halogen oxoacids such ashypochloric acid, chloric acid, perchloric acid, periodic acid; sulfuricacid; boric acid; nitric acid, phosphoric acid, etc.); sulfonic acids(e.g., methanesulfonic acid, p-toluenesulfonic acid); solid bound protondonors (e.g., Amberlyst 15, Amberlyst 35, and the like); ion exchangeresins (e.g., Amberlite, Amberjet, Dowex, etc.); ionomers (e.g.,polystyrene sulfonate, Nafion, Hycar and so forth); and ionic liquidshaving acidic characteristics.

The mole-to-mole ratio of the compound of Formula (III) to the protondonor catalyst can and will vary depending upon the identity of theproton donor. In general, the mole-to-mole ratio of the compound havingFormula (III) to the proton donor may range from about 1:0.005 to about1:0.25. In some embodiments, the mole-to-mole ratio of the compound ofFormula (III) to the proton donor may be about 1:0.01, about 1:0.02,about 1:0.04, about 1:0.05, about 1:0.06, about 1:0.08, about 1:0.10,about 1:0.12, about 1:0.14, about 1:0.16, about 1:0.18, or about 1:0.20.

The reaction may be conducted in the absence of a solvent or in thepresence of a solvent. In embodiments in which a solvent is present, thetype of solvent may vary depending upon the reactants. Thus, the solventmay be a nonpolar solvent, a polar solvent, or a combination thereof.Non-limiting examples of suitable nonpolar solvents include benzene,butyl acetate, tert-butyl methyl ether, chlorobenzene, chloroform,chloromethane, cyclohexane, dichloromethane (DCM), dichloroethane,di-tert-butyl ether, dimethyl ether, diethylene glycol, diethyl ether,diglyme, diisopropyl ether, ethyl tert-butyl ether, ethylene oxide,fluorobenzene, heptane, hexane, methyl tert-butyl ether, toluene, andcombinations thereof. Non-limiting examples of suitable polar solventsinclude acetone, acetonitrile, diethoxymethane, N,N-dimethylformamide(DMF), dimethyl sulfoxide (DMSO), N,N-dimethylpropionamide,1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU),1,3-dimethyl-2-imidazolidinone (DMI), 1,2-dimethoxyethane (DME),dimethoxymethane, bis(2-methoxyethyl)ether, N,N-dimethylacetamide(DMAC), N-methyl-2-pyrrolidinone (NMP), 1,4-dioxane, ethyl acetate,ethyl formate, formamide, hexachloroacetone, hexamethylphosphoramide,methyl acetate, N-methylacetamide, methylethyl ketone, methylisobutylketone, N-methylformamide, methylene chloride, methoxyethane,morpholine, nitrobenzene, nitromethane, propionitrile, propyl acetates,sulfolane, tetramethylurea, tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, trichloromethane, and combinationsthereof. In specific embodiments, the solvent may be toluene.

The volume-to-mass (i.e., mL to g) ratio of the solvent to the compoundof Formula (III) can and will vary. Typically, the volume-to-mass ratioof the solvent to the compound of Formula (III) may range from about 1:1to about 100:1. In various embodiments, the volume-to-mass ratio of thesolvent to the compound of Formula (III) may range from about 1:1 toabout 3:1, from about 3:1 to about 10:1, from about 10:1 to about 30:1,or from about 30:1 to about 100:1.

The reaction may be conducted at a temperature that ranges from about30° C. to about 200° C. In certain embodiments, the temperature of thereaction may be about 40° C., 50° C., 60° C., 70° C., 80° C., 90° C.,100° C., 110° C., 120° C., 130° C., 140° C., or 150° C. In specificembodiments, the reaction may be conducted at a temperature from about80° C. to about 150° C.

The duration of the reaction can and will vary. In general, the reactionmay be allowed to proceed from about 1 hour to about 24 hours or more.In some embodiments, the reaction may be allowed to proceed overnight(or from about 12 to about 18 hours). Typically, however, the reactionis allowed to proceed for a sufficient period of time until the reactionhas proceeded to the desired degree of completion, as determined bymeans well known to those of skill in the art. In embodiments in whichthe reaction is allowed to go to completion, a “completed reaction”generally means that the final reaction mixture contains a significantlydiminished amount of the compound comprising Formula (III) and asignificantly increased amount of the ester compound comprising Formula(II) compared to the amounts of each present at the beginning of thereaction.

The compounds of Formula (II) may be isolated from the reaction mixtureby means known in the art. Suitable means include extracting, washing,precipitating, filtering, distilling, evaporating, drying,chromatography, and combinations thereof.

The yield of the compounds of Formula (II) can and will vary. Ingeneral, yield of the compounds will be at least about 20%, at leastabout 30%, at least about 40%, at least about 50%, at least about 60%,at least about 70%, at least about 80%, or at least about 90%.

(b) Step A—Ring Opening Polymerization

In other embodiments, the esterification and polymerization step isperformed by a ring opening polymerization reaction. For this, acompound having Formula (IV) is contacted with an alcohol, R³OH, to forma distribution of compounds having Formula (II) in which k varies. Thereaction is diagrammed below:

wherein R¹, R³, Z, k, and n are as defined above in section (I).

The ring opening polymerization reaction comprises contacting the cycliccompound having Formula (IV) with an alcohol (R³OH). In general, themole-to-mole ratio of the compound of Formula (IV) to R³OH may rangefrom about 1:0.1 to about 1:2. In various embodiments, the mole-to-moleratio of the compound of Formula (IV) to R³OH may range from about 1:0.2to about 1:1, from about 1:0.3 to about 1:0.9, from about 1:0.4 to about1:0.8, or from about 1:0.5 to about 1:0.7.

In general, contact between the compound having Formula (IV) and thealcohol is conducted in the presence of a catalyst. Suitable catalystsand amounts to be included in the reaction mixture are detailed above insection (IV)(a). The reaction may be conducted in the absence orpresence of a solvent, examples of which are detailed above in section(IV)(a). Suitable reaction temperatures, reaction times, optionalisolation methods, and yields are described above in section (IV)(a).

(c) Step B—Esterification

In some embodiments, Step B comprises an esterification reaction. Forthis, the distribution of compounds of Formula (II) is contacted with anacyl halide or its acid analog, R⁴C(O)X, to form a distribution ofcompounds of Formula (Ia), as shown below:

wherein R¹, R³, Z, n, and k, are as defined above in section (I); R⁴ ishydrocarbyl or substituted hydrocarbyl; and X is a halide ion or ahydroxyl group. When X is a hydroxyl group, R⁴C(O)X may be a fatty acidor a carboxylic acid. In specific embodiments, X may be chloride orbromide.

The amount of R⁴C(O)X that is contacted with the compounds of havingFormula (II) can and will vary. In general, the mole-to-mole ratio ofthe compounds of Formula (II) to R⁴C(O)X may range from about 1:0.8 toabout 1:1.5. In various embodiments, the mole-to-mole ratio of thecompounds of Formula (II) to the R⁴C(O)X may range from about 1:0.9 toabout 1:1.4, from about 1:1.0 to about 1:1.3, or from about 1:1.1 toabout 1:1.2.

The reaction may be conducted in the absence of a solvent or in thepresence of a solvent. In embodiments in which a solvent is present,suitable solvents are listed above in section (IV)(a).

The reaction may be conducted at a temperature that ranges from about30° C. to about 200° C. In certain embodiments, the temperature of thereaction may be about 40° C., 50° C., 60° C., 70° C., 80° C., 90° C.,100° C., 110° C., 120° C., 130° C., 140° C., or 150° C. In specificembodiments, the reaction may be conducted at a temperature from about70° C. to about 90° C. In general, the reaction will be conducted atatmospheric pressure.

The duration of the reaction can and will vary. In general, the reactionmay be allowed to proceed from about 1 hour to about 24 hours or more.In some embodiments, the reaction may be allowed to proceed overnight(or from about 12 to about 18 hours). Typically, however, the reactionis allowed to proceed until the compound having Formula (II) is nolonger detectable.

The compounds comprising Formula (Ia) may be isolated from the reactantsin the reaction mixture by means known in the art. Suitable meansinclude extracting, washing, precipitating, filtering, distilling,evaporating, drying, chromatography, and combinations thereof.

The yield of the compounds comprising Formula (Ia) can and will vary. Ingeneral, yield of the compound will be at least about 20%, at leastabout 30%, at least about 40%, at least about 50%, at least about 60%,at least about 70%, at least about 80%, or at least about 90%.

(d) Step B—Alkylation

In alternate embodiments, Step B comprises an alkylation reaction. Forthis, the compound(s) having Formula (II) is contacted with analkylating agent, R⁴L, to form a compound(s) having Formula (Ib), asshown below

wherein R¹, R³, Z, n, and k are as defined above in section (I); R⁴ ishydrocarbyl or substituted hydrocarbyl; and L is a leaving group.Suitable leaving groups include halide ions (such as chloride, bromide,etc.) and sulfonate esters (such as tosylate, mesylate, and the like).

The amount of the alkylating agent (R⁴L) that is contacted with thecompounds of Formula (II) can and will vary. In general, themole-to-mole ratio of the compounds having Formula (II) to thealkylating agent may range from about 1:0.1 to about 1:10. In variousembodiments, the mole-to-mole ratio of the compounds having Formula (II)to the alkylating agent (R⁴L) may range from about 1:01 to about 1:0.3,from about 1:0.3 to about 1:1, from about 1:1 to about 1:3, or fromabout 1:3 to about 1:10.

The reaction may be conducted in the absence of a solvent or in thepresence of a solvent. In embodiments in which a solvent is present,suitable solvents are listed above in section (IV)(a). Suitable reactiontemperatures, reaction times, optional isolation methods, and yields aredescribed above in section (IV)(c).

(e) Optional Oxidation Reaction

In embodiments in which Z is sulfur in any of the compounds disclosedabove, the compound(s) may undergo one or more oxidation reactions toconvert Z into a sulfoxide or a sulfone.

A variety of oxidizing agents may be used in this process. Non-limitingexamples of suitable oxidizing agents include peroxy acids (e.g.,chloroperoxybenzoic acid, peracetic acid, peroxysulfuric acid), hydrogenperoxide, perchlorates, chlorite, hypochlorite, chlorate, sulfuric acid,persulfuric acid, hexavalent chromium compounds, permanganate compounds,sodium perborate, nitric acids, nitrate compounds, metal oxidants (suchas, e.g., benezeneselenic acid, lead tetraacetate, osmium tetroxide,phosphomolybdic acid hydrate, pyridinium chlorochromate, pyridiniumdichromate, quinolinium dichromate, and the like). and combinationsthereof. In preferred embodiment, the oxidizing agent may bem-chloroperoxybenzoic acid or hydrogen peroxide.

The mole-to-mole ratio of the compound(s) of Formula (I), (Ia), (Ib)(II), (III), or (IV) to the oxidizing agent can and will vary. Ingeneral, the mole-to-mole ratio of the compound to the oxidizing agentmay range from about 1:0.1 to about 1:20, from about 1:0.2 to about1:10, from about 1:0.5 to about 1:5, or from about 1:1 to about 1:3.

The oxidation reaction may be performed in the presence of a solvent.The solvent may be a nonpolar solvent, a protic solvent, or an aproticsolvent depending upon the nature of the reactants. Suitable solventsare detailed above. The volume-to-mass ratio of the solvent to thecompound of Formula (I), (Ia), (Ib) (II), (III), or (IV) can and willvary. Typically, the volume-to-mass ratio of the solvent to the compoundmay range from about 1:1 to about 60:1. In various embodiments, thevolume-to-mass ratio of the solvent to the compound may range from about4:1 to about 40:1.

The oxidation reaction may be conducted at a temperature that rangesfrom about −10° C. to about 50° C. In certain embodiments, thetemperature of the reaction maybe about 0° C., about 10° C., about 20°C., about 25° C., or about 30° C. In one embodiment, the reaction may beallowed to proceed at about 00° C. In another embodiment, the reactionmay be allowed to proceed for a first period of time at 00° C. and asecond period of time at room temperature. In still another embodiment,the reaction may be conducted at room temperature. Typically, thereaction will be conducted at atmospheric pressure.

The duration of the reaction can and will vary. In general, the reactionmay be allowed to proceed from several hours to several days. Typically,however, the reaction may be allowed to proceed for a sufficient periodof time until the reaction is complete or substantially complete, asdetermined by means well known to those of skill in the art.

The compositions prepared according to the disclosures above can beoptionally treated with one or more agents to remove color bodies and/orodor. Persons skilled in the art understand that a variety of differentagents may be used to remove color bodies and/or odor from thecompositions disclosed herein. In specific embodiments, the agent ischarcoal.

Definitions

When introducing elements of the embodiments described herein, thearticles “a”, “an”, “the” and “said” are intended to mean that there areone or more of the elements. The terms “comprising”, “including” and“having” are intended to be inclusive and mean that there may beadditional elements other than the listed elements.

The terms “elongation” or “tensile elongation,” as used herein, refer toa mechanical property of a polymer to deform or change shape when undertensile stress. When a polymer sample deforms by stretching, it becomeslonger. Elongation is the percentage increase in original length.Elongation at yield refers to the point at which an increase in straindoes not result in an increase in stress. “Elongation at break”corresponds to the point of rupture.

The “glass transition temperature” is the temperature at which a polymertransitions from a hard, glassy material to a soft, rubbery material.

The “cold crystallization temperature” is the temperature at which apolymer crystallizes.

As used herein, the term “pristine polymer” refers to a polymer that isdevoid of additives.

The terms “tensile modulus” or “Young's modulus” refer to the stiffnessof a material, and are used to describe the elastic properties of thematerial. Tensile modulus is defined as the ratio of stress (force perunit area) along an axis to strain (ratio of deformation over initiallength) along that axis.

The term “tensile strength at break” refers to the tensile stress at themoment at which a test sample breaks. Tensile strength is the forceplaced on the test sample divided by the cross-sectional area of thesample.

The term “acyl,” as used herein alone or as part of another group,denotes the moiety formed by removal of the hydroxyl group from thegroup COOH of an organic carboxylic acid, e.g., RC(O)—, wherein R is R¹,R¹O—, R¹R²N—, or R¹S—, R¹ is hydrocarbyl, heterosubstituted hydrocarbyl,or heterocyclo, and R² is hydrogen, hydrocarbyl, or substitutedhydrocarbyl.

The term “acyloxy,” as used herein alone or as part of another group,denotes an acyl group as described above bonded through an oxygenlinkage (O), e.g., RC(O)O— wherein R is as defined in connection withthe term “acyl.”

The term “alkyl” as used herein describes saturated hydrocarbyl groupsthat contain from 1 to 30 carbon atoms. They may be linear, branched, orcyclic, may be substituted as defined below, and include methyl, ethyl,propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, and the like.

The term “alkenyl” as used herein describes hydrocarbyl groups whichcontain at least one carbon-carbon double bond and contain from 1 to 30carbon atoms. They may be linear, branched, or cyclic, may besubstituted as defined below, and include ethenyl, propenyl,isopropenyl, butenyl, isobutenyl, hexenyl, and the like.

The term “alkoxide” or “alkoxy” as used herein is the conjugate base ofan alcohol. The alcohol may be straight chain, branched, cyclic, andincludes aryloxy compounds.

The term “alkynyl” as used herein describes hydrocarbyl groups whichcontain at least one carbon-carbon triple bond and contain from 1 to 30carbon atoms. They may be linear or branched, may be substituted asdefined below, and include ethynyl, propynyl, butynyl, isobutynyl,hexynyl, and the like.

The term “aromatic” as used herein alone or as part of another groupdenotes optionally substituted homo- or heterocyclic conjugated planarring or ring system comprising delocalized electrons. These aromaticgroups are preferably monocyclic (e.g., furan or benzene), bicyclic, ortricyclic groups containing from 5 to 14 atoms in the ring portion. Theterm “aromatic” encompasses “aryl” groups defined below.

The term “aryl” as used herein alone or as part of another group denoteoptionally substituted homocyclic aromatic groups, preferably monocyclicor bicyclic groups containing from 6 to 10 carbons in the ring portion,such as phenyl, biphenyl, naphthyl, substituted phenyl, substitutedbiphenyl, or substituted naphthyl.

The terms “halogen” or “halo” as used herein alone or as part of anothergroup refer to chlorine, bromine, fluorine, and iodine.

The term “heteroatom” refers to atoms other than carbon and hydrogen.

The term “heteroaromatic” as used herein alone or as part of anothergroup denotes optionally substituted aromatic groups having at least oneheteroatom in at least one ring, and preferably 5 or 6 atoms in eachring. The heteroaromatic group preferably has 1 or 2 oxygen atoms and/or1 to 4 nitrogen atoms in the ring, and is bonded to the remainder of themolecule through a carbon. Exemplary groups include furyl, benzofuryl,oxazolyl, isoxazolyl, oxadiazolyl, benzoxazolyl, benzoxadiazolyl,pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl,pyrimidyl, pyrazinyl, pyridazinyl, indolyl, isoindolyl, indolizinyl,benzimidazolyl, indazolyl, benzotriazolyl, tetrazolopyridazinyl,carbazolyl, purinyl, quinolinyl, isoquinolinyl, imidazopyridyl, and thelike. Exemplary substituents include one or more of the followinggroups: hydrocarbyl, substituted hydrocarbyl, alkyl, alkoxy, acyl,acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal,carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo,hydroxyl, keto, ketal, phospho, nitro, and thio.

The terms “heterocyclo” or “heterocyclic” as used herein alone or aspart of another group denote optionally substituted, fully saturated orunsaturated, monocyclic or bicyclic, aromatic or non-aromatic groupshaving at least one heteroatom in at least one ring, and preferably 5 or6 atoms in each ring. The heterocyclo group preferably has 1 or 2 oxygenatoms and/or 1 to 4 nitrogen atoms in the ring, and is bonded to theremainder of the molecule through a carbon or heteroatom. Exemplaryheterocyclo groups include heteroaromatics as described above. Exemplarysubstituents include one or more of the following groups: hydrocarbyl,substituted hydrocarbyl, alkyl, alkoxy, acyl, acyloxy, alkenyl,alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo,cyano, ester, ether, halogen, heterocyclo, hydroxyl, keto, ketal,phospho, nitro, and thio.

The terms “hydrocarbon” and “hydrocarbyl” as used herein describeorganic compounds or radicals consisting exclusively of the elementscarbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, andaryl moieties. These moieties also include alkyl, alkenyl, alkynyl, andaryl moieties substituted with other aliphatic or cyclic hydrocarbongroups, such as alkaryl, alkenaryl and alkynaryl. They may be straight,branched, or cyclic. Unless otherwise indicated, these moietiespreferably comprise 1 to 20 carbon atoms.

The “substituted hydrocarbyl” moieties described herein are hydrocarbylmoieties which are substituted with at least one atom other than carbon,including moieties in which a carbon chain atom is substituted with aheteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or ahalogen atom, and moieties in which the carbon chain comprisesadditional substituents. These substituents include alkyl, alkoxy, acyl,acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal,carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo,hydroxyl, keto, ketal, phospho, nitro, and thio.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following examples illustrate various embodiments of the invention.

Example 1: Polyester Composition with End Ethylhexyl Groups Prepared byCondensation

Step A.

To 2-hydroxy-4-(methylthio)butanoic acid (88%, 60.4 g, 354 mmol) wasadded 2-ethyl-1-hexanol (41.5 g, 319 mmol), and Amberlyst 15 (6.10 g).The resulting mixture was heated under vacuum (53 mbar) with removal ofwater by raising the jacket temperature to 90° C. over the course of 1hour. The jacket temperature was held at 90° C. for 10.5 hrs and thenthe vacuum was released and the reaction was cooled to room temperature,diluted with ethyl acetate (200 mL), and filtered. The solution was thenwashed with 5% sodium bicarbonate (2×50 mL), brine (3×50 mL), dried overmagnesium sulfate, filtered and evaporated to give a yellow oil (80.1 g,90%).

Step B.

The mixture obtained above (67 g) and 2-ethylhexanoyl chloride (43 g)were mixed together. The mixture was slowly heated to 80° C. to controlthe gas evolution. The mixture was held at 80° C. until the octyl2-hydroxy-4-(methylthio)butanoate was consumed. The mixture then wascooled to 25° C. and 1 M aqueous NaOH (100 mL) was added. The mixturewas stirred until the excess 2-ethylhexanoyl chloride was quenched.Methyl tert-butyl ether (100 mL) was added and the phases wereseparated. The organic phase was washed with water (100 mL) followed bybrine (100 mL). The organic phase was dried and the solvent was removedby distillation under reduced pressure at 50° C. using a rotaryevaporator. An orange-colored, viscous liquid (93 g) was obtained,comprising a mixture of 98% of compounds of Formula (I) in which kranged from 1 to 4.

Example 2: Polyester Compound with End Decyl Groups Prepared byCondensation

Step A.

To a 4 neck 1 L round bottom flask fitted with a reflux condenser, deanstark trap, thermocouple, and mechanical overhead stirrer was added2-hydroxy-4-(methylthio)butanoic acid (125 g, 832.2 mmol), 1-decanol(238 mL, 1248 mmol), sodium hydrogen sulfate (1.998 g, 16.64 mmol), andtoluene (625 mL). The reaction was heated to reflux with removal ofwater (16 mL) during the course of about 6 hours and the reaction wasmonitored by GC analysis. The reaction was cooled to room temperatureovernight and the organic layer was washed with saturated NaHCO₃ (1×300mL), deionized water (1×300 mL), and brine (2×300 mL), dried over sodiumsulfate, filtered and evaporated to give an amber oil (395.5 g). The oilwas purified by kugelrohr distillation at 110° C. and 0.1 Torr vacuum togive an oil (105.2 g, 44%) comprising the monomer. m/z 313 (MNa⁺)

Step B.

To the monomer prepared above (decyl 2-hydroxy-4-(methylthio)butanoate;20.0 g, 69.0 mmol) was added 1-decanoyl chloride (16.5 mL, 79.5 mmol)and the solution was slowly heated to 80° C. to control the gasevolution. The mixture was held at 80° C. until the decyl2-hydroxy-4-(methylthio)butanoate was consumed. The mixture was cooledto 25° C. and 1 M aqueous NaOH (30 mL) was added. The mixture wasstirred until the excess 2-ethylhexanoyl chloride was quenched. Methyltert-butyl ether (50 mL) was added and the phases were separated. Theorganic phase was washed with water (30 mL) followed by brine (30 mL).The organic phase was dried and the solvent was removed by distillationunder reduced pressure at 50° C. using a rotary evaporator to give alight yellow liquid (31.4 g, quantitative) (m/z 467 (MNa⁺), whichconsisted of 97% of the compound having Formula (I) in which k=1.

Example 3: Polyester Composition with End Ethylhexyl Groups Prepared byRing Opening Polymerization (ROP)

Step A.

3,6-Bis[2-(methylthio)ethyl]-1,4-dioxane-2,5-dione (50 g, 189 mmol) and2-ethyl-1-hexanol (24.7 g, 189 mmol) were dissolved in toluene (200 mL).3 Å molecular sieves (20 g) and Amberlyst-15 (5 g) were added and themixture was heated at 60° C. for several hours. The resin was filteredoff and the toluene was removed using a rotary evaporator.

Step B.

2-Ethylhexanoyl chloride (31.4 g, 193 mmol) was added to the productfrom Step 1, and the mixture was slowly heated to 80° C. to control thegas evolution. The mixture was held at 80° C. until the 2-ethylhexyl2-((2-hydroxy-4-(methylthio)butanoyl)oxy)-4-(methylthio)butanoate wasconsumed. The mixture was cooled to 25° C. and 1 M aqueous NaOH (200 mL)was added. The mixture was stirred until the excess 2-ethylhexanoylchloride was quenched. Methyl tert-butyl ether (200 mL) was added andthe phases were separated. The organic phase was washed with water (100mL) followed by brine (100 mL). The organic phase was dried and thesolvent was removed by distillation under reduced pressure at 50° C.using a rotary evaporator. An orange-colored, viscous liquid (91 g) wasobtained comprising 91% of compound of Formula (I) with k=2 and 9% ofother oligomeric compounds of Formula (I).

Example 4: Polyester Composition (Mn=800) Prepared by ROP

A 500 ml flask thermostated at 70° C. was charged with melted 3,6-bis(2-methylthio)ethyl-1,4-dioxane-2,5 dione (120.2 g, 454 mmol) under N₂and a stirring bar. The system was completely flushed with dry N₂ for0.5 hours. Then 1-octanol (36.1 mL, 29.75 g, 228 mmol) was added intothe reactor, followed by addition of 0.01 ml of stannous octoatecatalyst. The temperature of the system was raised to and maintained at140° C. for about 9 hours. Analysis of the product gave Mn=770 g/mol,PDI=1.17, and consisted to 100% of compound of Formula (R²═H) with kfrom 1 to 12.

Example 5: Polyester Composition (Mn=600) Prepared by ROP

Into a 500 ml flask was charged with melted 3,6-bis(2-methylthio)ethyl-1,4-dioxane-2,5 dione (197.4 g, 746 mmol) under N₂and a stirring bar. The system was completely flushed with dry N₂ for0.5 hours. The flask was thermostated at 70° C. Then 1-octanol (79.5 mL,65.5 g, 503 mmol) was added into the reactor, followed by addition of0.016 ml of stannous octoate catalyst. The temperature of the system wasraised to and maintained at 140° C. for about 3.5 hours. Analysis of theproduct gave Mn=590 g/mol, PDI=1.15, and consisted of 100% of compoundof Formula (I) (R²═H) with k from 1 to 10.

Example 6: Polyester Composition with End Octyl Groups Prepared by ROP

An aliquot (50.2 g) of the product from Example 5 was weighed into a2-necked 250 mL round bottom flask. A stir bar was added and the flaskwas equipped with a temperature probe and an external scrubber for HCloff gassing. Octanoyl chloride (18.6 mL; 17.74 g; 109.1 mmol) was addedto the flask and the reaction was slowly warmed to 80° C., whilestirring, under N₂ purge, for 16-18 hours. The reaction was cooled toroom temperature and treated with 50 mL of 1 M NaOH, and stirred underN₂. After 3 hours, 100 mL of methyl t-butyl ether was added and thelayers separated. The aqueous layer was extracted once with 50 mL ofmethyl t-butyl ether and the organic layers were combined, washed withbrine, dried over magnesium sulfate, filtered and concentrated to aclear light colored oil. The oil was dried on high vacuum line for 16-18hours to give 63.01 g of a clear light yellow colored oil consisting of100% of compound of Formula (I) with k from 1 to 10.

Example 7: Preparation of PLA Blends

Polymer blend compositions comprising PLA and the product from Example4, Example 5, dioctyl adipate (DOA), or acetyl tributyl citrate (ATBC),were respectively prepared. Table 1 lists the compositions of PLA blends1-5.

TABLE 1 PLA Blends Blend PLA Wt % Mass Plasticizer Wt % Mass 1 Ingeo4032D 80 1.6274 g Example 4 20 0.4066 g 2 Ingeo 4032D 75 1.5668 gExample 5 25 0.5124 g 3 Ingeo 4032D 80 1.6379 g DOA 20 0.4044 g 4 Ingeo4032D 80 1.7248 g ATBC 20 0.4365 g 5 Ingeo 3251D 80 1.6708 g Example 420 0.414 gThe blends were prepared by dissolving the PLA resin and plasticizer inabout 15 ml of anhydrous dichloromethane in a 40 ml vial. The solutionwas placed on a shaker to facilitate the dissolution over several days.Then the solution was poured on to a glass plate and solvent wasevaporated. The film was thoroughly dried in a vacuum oven.Thermogravimetric analysis (TGA) showed less than 0.5% of residualsolvent was detected.

Example 8: Evaluation of Plasticization and Acceleration ofCrystallization of PLA Blends

To evaluate the plasticization efficiency of the compounds disclosedherein, the glass transition temperature (Tg) and crystallization rateof PLA were evaluated by differential scanning calorimetry (DSC).Depression of T_(g) is an indication of plasticization to show theincreased polymer chain mobility. Crystallinity is a critical propertyin the application of PLA. In injection molding, the time it takes forpure PLA to develop a certain level of crystallinity in order to havehigh enough modulus and heat resistance for practical use is too long.Plasticizers/accelerants accelerate the crystallization rate of PLA bylowering the cold crystallization temperature (T_(cc)). Table 2 presentsT_(g), T_(cc), and T_(m) of pure PLA and the PLA blends prepared inExample 7.

TABLE 2 Plasticization and Acceleration of Crystallization of PLA PLAPLA PLA PLA PLA PLA PLA 3251D 4032D Blend 1 Blend 2 Blend 3 Blend 4Blend 5 T_(g) 57.6 56.4 29.8 22.2 42.5 20.6 31.1 (° C.) T_(cc) 105.1136.7 69.6 58.5 87.8 80.5 72.4 (° C.) T_(m) 168.9 166.2 162.7 161.1 162160.5 163 (° C.)

The data show that the compounds disclosed herein (i.e., Blends 1, 2,and 5) efficiently plasticized PLA by significantly decreasing T_(g) ofPLA. The decrease in T_(g) is comparable to the that of traditionalplasticizers such as DOA and ATBC. Furthermore, T_(cc) of the blendscomprising the compounds disclosed herein were as low as 69.6° C., muchlower than that of the traditional accelerants DOA and ATBC, whenincluded at the same inclusion rate of 20 wt %.

Example 9: Evaluation of the Mechanical Properties of PLA Blends

Blends of PLA and plasticizers were prepared using a Brabender mixer andthe mixture was compression molded into films of 0.26 mm at 190° C. PLAblend 6 contained 85 wt % PLA (Ingeo 4060D) and 15 wt % of 3,6-bis(2-methylthio)ethyl-1,4-dioxane-2,5 dione. PLA blend 7 contained 80 wt %PLA (4032D) and 20 wt % of the product from Example 4.

The molded films were tested with dynamic-mechanical thermal analysis(DTMA) and tensile tester for mechanical properties per ASTM D882. Ascontrols, pure PLA was processed under the same compounding and moldingconditions described above. Table 3 presents the data.

TABLE 3 Mechanical properties of PLA Tensile Elongation at T_(g) T_(cc)Strength at Yield Break Modulus Sample (° C.) (° C.) Yield (MPa) (%) (%)(KPSI) PLA alone 63 — 27.6 4.6 6.0 124.8 (Ingeo 4060D) PLA Blend 6 40.018.6 4.1 44.2 121 PLA alone 67.5 120 42.5 4.3 5.3 133.5 (Ingeo 4032D)PLA Blend 7 20.8 80.4 33.2 5.9 288.6 81.4

The plasticizers disclosed herein increased plasticity (i.e., loweredT_(g) and T_(cc)) and increased elongation at break, while maintaininggood tensile strength and modulus. The increase in flexibility wassignificant; e.g., PLA blend 7 increased elongation at break by morethan 50-fold and PLA blend 6 increased elongation at break by about7-fold.

Example 10: Evaluation of the Mechanical Properties of PVC Blends

Polymer blend compositions comprising PVC and the product of Examples 5,Example 3, or diisononyl phthalate (DINP) were prepared. Theplasticizers were evaluated at two inclusion rates (i.e., 20 or 50 partsper hundred parts of resin (pphr)). Each blend also contained antimonytrioxide (3 parts), calcium zinc stabilizer (8 parts), stericallyhindered phenolic antioxidant (Irganox 1010) (1 part), and epoxidesoybean oil (3 parts). Table 4 lists the compositions of the PVC blends.

TABLE 4 PVC Blends Plasticizer PVC Blend Plasticizer (pphr) (parts) 1DINP 20 100 2 DINP 50 100 3 Example 5 20 100 4 Example 5 50 100 5Example 3 20 100 6 Example 3 50 100 7 Example 1 50 100 8 Example 2 50100 9 Example 6 50 100

The mechanical properties of the PVC blends were tested per ASTM D882.Table 5 presents the results.

TABLE 5 Mechanical properties of PVC Blends Tensile Strength (KPSI) at100% Elongation Modulus Material Break Elongation at Break (%) (KPSI)PVC Blend 1 1.88 60.9 17.1 PVC Blend 2 1.67 1.25 281.2 1.74 PVC Blend 33.29 — 207.6 46.2 PVC Blend 4 2.09 1.38 340.6 1.75 PVC Blend 5 3.34 —245.4 46.2 PVC Blend 6 1.98 0.63 347.5 2.98 PVC Blend 7 1.60 — 318.81.08 PVC Blend 8 1.39 — 369.0 0.72 PVC Blend 9 2.23 — 341.6 2.22

These data show that the plasticizers disclosed herein significantlyimproved flexibility of PVC for plasticization meanwhile maintaining agood tensile strength and modulus. These plasticizers outperform theindustry standard DINP for tensile properties.

What is claimed is:
 1. A process for preparing a distribution ofcompounds of Formula (Ia) from a compound of Formula (III), the processcomprising: (a) contacting the compound of Formula (III) with analcohol, R³OH, to form a distribution of compounds of Formula (II); and

(b) contacting the distribution of compounds of Formula (II) with anacyl halide or its acid analog, R⁴C(O)X, to form the distribution ofcompounds of Formula (Ia);

wherein: R¹, R³, and R⁴ independently are hydrocarbyl or substitutedhydrocarbyl; X is a halide ion or a hydroxyl group; Z is sulfur,sulfoxide, or sulfone; k is an integer of 1 or greater; and n is aninteger of 1 or greater.
 2. The process of claim 1, wherein R¹ is alkyl;and R³ and R⁴ independently are alkyl, substituted alky, alkenyl, orsubstituted alkenyl.
 3. The process of claim 1, wherein R¹ is C₁ to C₆alkyl; and R³ and R⁴ independently are C₁ to C₃₀ alkyl or C₁ to C₃₀alkenyl.
 4. The process of claim 3, wherein R¹ is methyl; Z is sulfur; kis from 1 to 20; and n is
 2. 5. The process of claim 1, wherein thecompound of Formula (III) and the alcohol, R³OH, are present at amole-to-mole ratio of about 1:0.1 to about 1:10;
 6. The process of claim1, wherein step (a) is conducted in the presence of a catalyst and at atemperature of about 80° C. to about 150° C.
 7. The process of claim 1,wherein the distribution of compounds of Formula (II) and R⁴C(O)X arepresent at a mole-to-mole ratio of about 1:0.8 to about 1:1.5.
 8. Theprocess of claim 1, wherein step (b) is conducted at a temperature ofabout 70° C. to about 90° C.
 9. The process of claim 1, furthercomprising contacting the distribution of compounds of Formula (Ia) withone or more agents to remove color bodies and/or odor.
 10. A process forpreparing a distribution of compounds of Formula (Ia) from a compound ofFormula (IV), the process comprising: (a) contacting the compound ofFormula (IV) with an alcohol, R³OH, to form a distribution of compoundsof Formula (II); and

(b) contacting the distribution of compounds of Formula (II) with anacyl halide or its acid analog, R⁴C(O)X, to form the distribution ofcompounds of Formula (Ia);

wherein: R¹, R³, and R⁴ independently are hydrocarbyl or substitutedhydrocarbyl; X is a halide ion or a hydroxyl group; Z is sulfur,sulfoxide, or sulfone; k is an integer of 1 or greater; and n is aninteger of 1 or greater.
 11. The process of claim 10, wherein R¹ isalkyl; and R³ and R⁴ independently are alkyl, substituted alky, alkenyl,or substituted alkenyl.
 12. The process of claim 10, wherein R¹ is C₁ toC₆ alkyl; and R³ and R⁴ independently are C₁ to C₃₀ alkyl or C₁ to C₃₀alkenyl.
 13. The process of claim 12, wherein R¹ is methyl; Z is sulfur;k is from 1 to 20; and n is
 2. 14. The process of claim 10, wherein thecompound of Formula (III) and the alcohol, R³OH, are present at amole-to-mole ratio of about 1:0.1 to about 1:10.
 15. The process ofclaim 10, wherein step (a) is conducted in the presence of a catalystand at a temperature of about 80° C. to about 150° C.
 16. The process ofclaim 10, wherein the compound of Formula (II) and R⁴C(O)X are presentat a mole-to-mole ratio of about 1:0.8 to about 1:1.5.
 17. The processof claim 10, wherein step (b) is conducted at a temperature of about 70°C. to about 90° C.
 18. The process of claim 10, further comprisingcontacting the distribution of compounds of Formula (Ia) with one ormore agents to remove color bodies and/or odor.